N-dihydro-azine compounds of the anthraquinone series and a process of preparing them



Patented Feb. 27, 1940 UNITED STATES PATENT OFFICE) N -DIHYDROAZINECOMPOUNDS OF THE AN THRAQUINONE SERIES AND A PROCESS OF PREPARING THEMGeorg Kranzlein, Ernst Diefenbach, and Fritz Eggert,Frankfort-on-the-Main-Hochst, Germany, assignors to General Aniline &Film Corporation, a corporation of Delaware No Drawing. ApplicationNovember 3, 1936, Sea rial No. 109,024. In Germany November 6,

and t z 0 nn -n-nn-x 3 XEN-RHN 0 2 wherein R. represents an aryl groupof the benzene series bound to the two NH-groups of the formula in orthopositions, X represents a member of the group consisting of aryl of thebenzene series, alkyl, hydroxyl alkyl, cyclo-alkyl and acyl, Yrepresents a member of the group consisting of sulfonic acid group andsulfonic amide group and Z represents a member ofthe group consisting ofhydrogen and bromine, with an aqueous or alcoholic solution of aninorganic acid or alkaline agent, for instance by stirring them togetherat room temperature or heating themif necessary to boiling. As suchsolution of acid or alkaline agents there may be used for instance:caustic soda solution, caustic potash solution, sodium. carbonatesolution, potassium carbonate solution, hydrochloric acid, sulfuricacid, phosphoric acid and the like. The solutions may be aqueous oralcoholic. The parent materials of the above formulae may be'obtained bycondensing an ortho-halogen-anthraquinone sulfonic acid ora derivativethereof which may contain further substituents in the anthraquinoneradical with an amine of the following general formula;

HaN NH.X

In this formula R means an aromatic radical,

in which the NI-Iaand NHX- groups stand in ortho-positionsto each other.The aromatic rad:

8 Claims. (Cl. 2 6026Z) ical B may contain substituents as well asaliphatic radicals or aromatic radicals of mononuclear, polynuclear orheterocyclickind, furthermore, nuclei which are combined with otheraliphatic or aromatic or heterocyclic radicals by 0112-, NH- or likebridges.

The X of the formula means an aliphatic or aromatic radical, which mayor may not contain substituents, for instance alkyl, aryl, aralkyl,

acyl, alkylsulfone, arylsulfone.

During the treatment of these condensation products with an alkaline oracid agent, the ring closure to the corresponding N-dihydro-azinesproceeds with separation of sulfurous acid, for instance according tothe following scheme:

wherein R and X have the above meaning.

The invention is essentially distinguished in many respects from thehitherto known processes. .1; When preparing the intermediate products,and closing the dihydro-azine ring it is possible to work in aqueoussolutions or suspensions and there is no need to isolate the ucts assuch. I

2. It is possible to form the dihydroaazine under mild conditions ofreaction, so that also sensitive amine components may be used.

3. Dyestufis of a hitherto unknown kind and.

many qualities may be obtained owing to the possibilities of wide choiceof the anthraquinone and amine components. According to the new processa great number of new substances is obtain-v able, for instance, thoseof the following general constitutions; V a

intermediate prod-7 and The follwing examples serve to illustrate theinvention, but they are not intended to limit it thereto; the parts areby weight:

(1) 20 parts of the compound 1:

(obtainable by reaction of ortho-aminodiphenylamine with1-bromanthraquinone-2-sulfonic acid in aqueous methyl alcohol of 25 percent. strength in the presence of sodium bicarbonate and. cu-

prous chloride) are dissolved in 2000 parts of water and the solution isheated to boiling after 'addition'of 100 parts of a caustic sodasolution of 35 per cent. strength. The boiling temperature is kept for10 minutes, the whole is acidified withhydrochloric acid and filteredwith, suction while hot. The finely crystalline dark-blue residue iswashed with hot water. The anthraquinone-1.2-dihydro-(N-phenyl)phenazine of the Formula 2 thus obtained is a dark blue powder whichdissolves in concentrated sulfuric acid to a yellow-green solution andyields a brown vat on addition of alkaline hydrosulfite. It dissolves inorganic solvents to a dark blue solution; it crystallizes from acetoneor glacial acetic acid in the form of fine blue needles with a bronzeluster, melting at 232 C.-233 C.

(2) When condensing l-bromanthraquinone-2- sulfonic acid with3-amino-l-methylamino-benzene-sulfonic acid, in the manner described inExample 1, there is obtained a brown-red solution I of the compound ofFormula 3 In order to close the dihydro-azine ring the clarifiedsolution is mixed with one-fifth of its volume of causticpotash solutionof 20 per cent. .20

strength and the whole is heated for one hour at C. to 0., whereby aftera shorttime;

the solution assumesan intensely blue color. The whole is allowed tocool, the separated prodnot is filtered with suction and washed with adilute solution of potassium chloride. The tassiumanthroquinone-L2-dihydro- (N-methyl) phenazine-sulfonate of the Formula4 thus obtained is a blue powder which dissolves in concentratedsulfuric acid to a green, in water to a blue, solution. From an acidbath there are obtained 0n wool greenish-blue tints of very goodproperties of fastness. The N-ethyl compound prepared in an analogousmanner has similar properties.

(3) A mixture of 25 parts of the condensation I product of the Formula 5COOH soln

coon

(obtainable by reaction of l-brom'anthraquinone 2-s'ulfonic acid with2-amino-2-carboxy-diphenylamine) and 1000 parts of an aqueous causticsoda solution of 3 per cent. strength, is heated to gentle boiling for ashort time. The deepblue solution produced is diluted with double itsweight of water and neutralized with acetic acid. On addition ofhydrochloric acid the dyestufi is precipitated in the form of blueflakes. It is 'filtered with suction and is thus obtained in the form ofa dark-blue powder whichdis solves in concentrated sulfuric acid to ayellow green solution. The dyestufi is suitable for the preparation ofvat-dyestufis.

(4) When 3-amino-4-hydroxyethylamino-benzene-sulfonic acid is condensedwith l-iodo-anthraquinone-2-sulfonic acid, in the manner described inExample 1, there is obtained a brownred' s'olution which is clarifiedand 'mixed'with caustic soda solution, the mixturebeing then haltd togentle'boiling until the'blue tint of the f5 l-NHI I l H 0 NH 0 solutionno longer changes: Thepur bluesolution obtained'is acidified" withdilute hydrochloric acid while hot. On cooling, the dyestufi of thefollowing constitution:

CHLOHl-OH precipitates in the form of long, fiatfblue prisms. Thedyestuff dyes wool-1n an acid ;bath'=a'green'- ish-blue tint of verygood properties 01. fastness.

(5) 20 parts of the. .condensation product of the Formula 8from"l-iodoeanthraquinoneeil-suh ionic acid andZ-amino-diphenylaminO:4+sul1 are suspended in 1000 parts of hydrochloricacid of 3 per cent. strength and the suspension is heated, whilestirring, to boiling "for a short while. The product is filtered withsuction while warm and washed with hydrochloric acid of 3 per cent.strength. The dyestufi thus obtained is a blue powder which-dyes wool;in- ;an acid bath very fast, clear, blue tints.

Instead of the hydrochloric acid of 3 per cent:

strength sulfuric acid of 5% strength or phosphonic acid may be used.

(6) 20 parts of the condensation product of the Formula 10: M

Hoas [l O p I NH 0 NH ----l H l H which is prepared by reaction of2-amino-di-' phenylamlne-4sulfonic acid with l-bromanthra-rquinone-2-sulfo-methyltauride are heated, while stirring to boiling in500 parts of. anaq ueous solution of hydrochloric acid uric-percent.

strength until the eparation of the a esmm precipitated-in the formof'blue flakes is terminated." The whole is then neutralized with asolutionei sodium carbonate of -10 per cent. strength and filtered withsuction; the product is purified by dissolving it in waterwandprecipitating it with hydrochloric acid.

(7-) Bycondensation of l-bromanthraquinone- 2-sulfonic"acid with2-ami-no-4'-chlorodiphenylamine t-sulfonic acid there is obtained avioletbrownsolution from which the condensation. product of Formula 12can be isolated only with: difliculty on account of its readysolubility.

When this solution is mixed with one-tenth of its volume of caustic sodasolution of 40 B.

and the whole is heated at 40 C. for one hour, 15

the dihydro-azine dyestuif of the Formula 13:

SO=Na 11 v I v e sOHH (l HN v 010 v I p p u N separates'in the form ofthin blue needles. The dyestufl dyes wool greenish-blue tints which aredistinguished by very good properties of fastness. v

' (8) In the same manner the dyestuif of the Formula. 15

14 s f l5 is obtained by condensing2-amino-4-dimethylairlinodiphenylamine-l-sulfonic acid with 1-halogenanthraquinone 2-sulfonic acid and heating to boiling the solutionof the primary condensation product of Formula 14 with dilute causticsoda solution for about one hour. From a blue solution the dyestufibegins to separate during the boiling 'in* the form of small blueneedles. After cooling, thewhole fllteredwith suction, re-washed withcold water and finally boiled out with dilute hydrochloric acid. The

dyestufi dyes wool greenish-blue tints of very good properties offastness.

(9) By condensation of 2-amino-4-sulfodiphenyl-amine-4-carboxylic acidwith l-halogenanthraquinone-Z-sulfonic acid in the manner described inExample 1 there is obtained a brownred solution of the condensationproduct of ,Formula 16:

. SOaH sonz- 00011 1 H NH 0 ll 1 I O I c0011 When this solution is mixedwith dilute caustic soda solution, the red-brown color changes to blueafter'about half-an-hour. The whole is stirred for about 12 hours at C.to 0., then mixed with hydrochloric acid and filtered with suction.

By redissolving in the usual manner there is obtained the dihydro-azinedyestuff of the Formula 17 in the form of a dark-blue powder. It dyeswool from an acid bath fast blue tints. If the amino-diphenylaminederivative without a sulfogroup is used there is obtained a bluedyestufi 40. which is suitable for the preparation of vat-dye- (10) Bycondensation of l-iodo-anth.raquinone-Z-sulfonic acid with2-amino-4-sulfodip-henyl-amino-2'-carboxylic acid in the mannerdescribed in Example 1 there is obtained a brownred solution of theintermediate product of the Formula 18:

In order to transform the intermediate product into the dihydro-azinederivative of the Formula 19 the solution is mixed with one-fifth of itsvolume of caustic soda solution of 40 B. and the temperature iskept at40 C. to 60 C. for 22 hours. The dyestuff is worked up as indicated inthe preceding example. It dyes wool from an acid bath blue tints of verygood properties of fastness.

(11) 1-bromanthraquinone-2-sulfonic acid is condensed with 2-amino-4f-acetylaminodipheny1- aminei-sulfonic acid in the manner. describedinExam le 1;; h ya i e rownsolutionr thedyestuff of the FormulaZO isobtained:

s0|H O @NTLCOJCH: SOaNa NH I g o IIIH SOrH This solution is clarified,mixed with dilute caustic soda solution and stirred atordinarytemperature for 48 hours, whereby thedihydroazine of the Formula21 gradually separates in the form of small blue crystals. The whole isfiltered with suction, washed with a dilute solution of sodium chloride,and the dyestufi isfinally purified by dissolving it in adilute solutionof sodium carbonate and precipitating it with hydrochloric acid. A bluepowder is obtained which dyes wool from an acid bath greenish-blue tintsof excellent properties of fastness. I 1

(12) If 25 parts of l-iodo-4-bromanthraquinone-:Z-sulfonic acid aremixed at'room temperature with. 17 parts of 2-amino-4-sulfodiphenylamine-4-hydroxy-3'-carboxy1ic acid'in the presi N Urmooom ence of 12parts of calcined sodium carbonate and 0.5 part of cuprous chloride inparts of water, a red-brown solution of thecondensation product of theFormula 22 is obtained oooH By gradually mixing this solution, whilestirring, at room temperature with a caustic soda solution of 35 percent. strength, the color is changed to a pure blue. after a shortwhile. Stirring is then continued until the color of the solution nolonger changes; the dyestufi of the Formula 23 which is formed, isseparated by addition of about 1000 parts of a solution of sodiumchloride of 3O per cent. strength. After filtration, the

product is washed with a solution of sodium chlo- I ride of 10 percent.'strength. For further purification, the productis dissolved inwater and. precipitated-by addition of dilute hydrochloric acid, I"

The dyestuff thus obtained dyes woo-l from an also be exchanged in knownmanner by amino radicals whereby a number of further new dye- 15 stufisis obtainable.

('13) 2'- amino 4 sulfodiphenylamine4'hydroxy-3'-carboxylic acid iscondensed with 1- bromanthraquinone-Z-sulfonic acid in the mannerdescribed in Example 1, whereby a brown- -violet solution of thecompound of the Formula 24 is obtained:

sous I 1 S0, coon 1 NH OH -N coon After filtration, thissolutionis mixedwith onequarter of its volume-of-causticsoda solution of 40 Be. andstirred. Aftera short while, the color of the solution has changed toblue. There- 45 upon, the whole is heated to 80 C- and mixed with sodiumchloride, whereupon the dyestufi of the Formula 25 is obtained in theform of a blue precipitate. The dyestuff dyes wool in an acid bathgreenish-blue tintsthe fastness of which Q may be further improved byafter-chroming.

(M) When 2-amino-4=-sulfodipheny1amino-5'- sulfo-2'hydroxy-3-carboxylicacid is condensed with l.-halogen-anthraquinone-2-sulfonic acid in themanner. described in Example ,1, the com:- 5,; pound of the Formula 26is obtained:

gradually becomes blue.

By mixing theaqueous solution of this compound with one-tenth of itsvolume of caustic soda solution of 40 Be. and stirring the whole at roomtemperature for some hours, the color of the solution becomesdeep-violet. When the color no longer changes, dilute hydrochloric acidis addedtonthe filtered solution until the product has completelyseparated in the form of violet flakes. The dyestuff thus obtained ofFormula 27 is a dark-violet powder which dissolves in con- 1 centratedsulfuric acid to a blue-green solution.

The acid as well as the after-chromed dyeing on' wool is violet.

() When 2 amino 2'-nitrodiphenylamine- 4"-sulfonic acid is condensedwith l-iodo-anthraquinone-2-sulfonic acid, in the manner described inExample 1, the compound of the Formula 28 'is' obtained:

'H 0 v NH SOaH 0 NO: I N

sonar Its aqueous solution is mixed with one-tenth of its Volume ofcaustic soda solution of per cent. strength and kept at gentle boilingfor about three hours. The dyestufi of the Formula 29 obtained in theform. of small blue needles is filtered with suction, washed with asolution of sodium chloride of 2 per cent. strength and dried. It dyeswool blue tints of very good fastness properties. By reduction of thenitro-group by means. of sodium sulfide a product is obtained whichyields on wool greenish-blue tints of likewise very good properties offastness.

(16) A mixture of 27 parts of potassium 1-iodoanthraquinone-2-sulfonate, 18 parts of 2-methylamino-3-amino-5-sulfobenzcic acid, 18 parts of calcined sodiumcarbonate and 1 part of cuprous chloride is stirred in 300 parts ofwater at room temperature for 18 hours. The mixture By working up thebatch, the dihydro-azine of the Formula 31 is obtained, as the primaryreaction product of the Formula 30 has already split ofi suliurous acidby the'action of the sodium carbonate.

coon

hydrochloric acid. "li'l'ie product thus obtained.

The dyestuff is isolated by introducing the clarifled blue solution,while stirring, into thrice its volume of a solution of sodium chlorideof 10 per cent. strength, acidifying with dilute hydrochloric acid,heating to boiling for a short while and filtering the separatedcompound With suction. It is obtained in the form of a dark-blue powderwhich dissolves in concentrated sulfuric acid to a green solution.

(17) 15 parts of the compound of the Formula 32 obtainable from1-iodoanthraquinone 2-su1- fonic acid and1-cyclohexylamino-2-aminobenzenel-sulfonic acid are dissolved in 1500parts of water and the solution is heated to boiling with 150 parts of acaustic soda solution of 35 per cent.

strength until the dihydro-azine dyestuff of the v Formula 33 hascompletelyseparated. The small gradual separation of dark-blue flakes.

while hot and washed with water. The product in the form of its alkalisalts dissolves in water to a reddish-blue solution. The color of thesolution in concentrated sulfuric acid is green-yellow.

$0511 SOx H 0 NH-cyclohexyl (I? S 03151 oyclohexyl in 2000 parts of acaustic soda solution of 1 per cent. strength and the solution isheated, while stirring, at 0. to 0. for some time. The

solution quickly becomes intensely blue with I When no more flakesseparate, the whole is filtered with suction, the solid matter is washedwith a dilute solution of sodium chloride; it constitutes the dyestuffand is purified by dissolving it in dilute caustic sodasolution andprecipitating it with NHCOCH:

son: w

(20) By condensing lmol. of sodiumlfi-d T hasthe Formula 35. .It.dissolves in concentrated tion of alkali-hydrosulfite, a brown-red vatis obtained. v

(19) 10 parts of the compound of the Formula 36, obtainable from1-iodoanthraquinone-2-suland Foder (cf. Annalenvol. 380,-page 324) sothat its mode of formation in the present example may be formulated asfollows:

n H o g 0 ll Nooont NH iodo-anthraquinone-2.6-disulfonate with 2 mols.of 2-amino-ldiphenyl-aminel-sul fonic acid, a, condensation product isobtained which corresponds with the Formula 39. By mixing the prod- Iuct with dilute caustic soda solution it may be transformed into adyestufi which probably has the constitution of the Formula 40; Itdissolves in water to a greendolue solution. The'solution inconcentrated sulfuric acid is yellow-green.

s9 soul The product yields on wool greenish-gray tints [of very goodproperties of fastnesst (21) In a manner similar to that described inExample there is obt-ainecLby condensation of sodium1.5-di-iodo-anthraquinone-2.6-disulfonate with 2 mols. of2-amino-4-su1fo-4'-hydroxy ,diphenyl-amine-3'-carboxylic acid, acompound of the Formula 41, which, when heated with dilute caustic sodasolution may be transformed into a dyestufi which probably correspondswith the Formula, 42:

smn

H coon O O I NH- on sotn nos 9' NH, coon coon \OH H000 The productdissolves in water to ablue solution and in concentrated sulfuric acidto a yellowgreen solution. With alkaline hydrosulfite solution anolive-green vat is obtained which, on further addition of hydrosulfite,turns to a brown-violet vat. From an acid solution there are obtained onwool greenish-blue dyeings which are capable of being after-chromed.

(22) In a similar manner there is obtained from the condensation productof sodium 1.5- dibromanthraquinone 2.6 disulfonate with 2 mols. of2-amino-4-sulfo-4'-acetaminodiphenylamine a compound which has probablythe constitution of the Formula 43:

CHICONH i NHOOOH i S 03H 43 It dissolves in water to a blue solution, inconcentrated sulfuric acid toa yellow-green solution and dyes wool fastblue tints.

Instead of the acetylvcompound there may also be'used any other arylcompound, for instance the benzoyl compound. A product with similarproperties is obtained.

We claim:

1.. The process which comprises treating with a condensing agent of thegroup consisting of aqueous and alcoholic solutions of inorganicalkalies and inorganic acids a member of the group consisting ofcompounds of the general formulae:

wherein R represents a member of the group consisting of phenyl andsubstituted phenyl radicals bound to the two NH-groups of the formula inortho positions, X represents 'a member of the group consisting ofphenyl and substituted phenyl radical, alkyl, hydroxy-alkyl, cycloalkyland acyl,

Y represents a member of the group consisting of sulfonic acid group andsulfonic amide group and Z represents a member .of 1 thegroup-consisting of hydrogen and bromine.

2. .The process which comprises treating with a condensing agent of thegroup consisting of.

5 'aqueous and alcoholic solutions of inorganic alkalies and inorganicacids .a compound of the general formula:

wherein R represents a member of the group consisting of phenyl andsubstituted phenyl radicals bound tothe two NH groups of the formula inortho positions, X represents a member of the 0 group consisting ofphenyl and substituted phenyl radicals, alkyl, hydroxy-alkyl, cycloalkyland acyl, Y represents a member of the group consisting of sulfonic acidgroup and sulfonic amide group and Z represents a member of :the groupconsisting of hydrogen and bromine.

3. The. process which comprises treating with a condensing agent of thegroup consisting of aqueous and alcoholic solutions of inorganicalkalies and inorganic acids a compound of the general formula YNHRNHXwherein R represents a member of the group consisting of phenyl andsubstituted phenyl radicals bound to the two NH- groups of the for-imula in ortho positions, X represents a member of the group consistingof phenyl and substituted ,phenyl radicals, alkyL-hydroxy-alkyl,cycloalkyl and acyl, Y represents a sulfonic acid group and Z representsa member of the group consisting ofhydrogen and bromine.

4. The process which comprises treating with .,an aqueous solution of acondensing inorganic alkali, a compound of the general formula:

0 NHR-l IHX wherein R represents a member of the group consisting ofphenyl andsubstituted phenyl radicals bound to the two NH-. groups ofthe forrnula in ortho position, X represents a member of the groupconsisting of phenyl and substituted phenyl radicals, alkyl,hydroxy-alkyl, cycloalkyl and acyl, Y represents a sulfonic acid groupand Z represents a member of the group consisting of hydrogen andbromine. Y 5. Theprocess which comprises treating with aquequs.solution. .oi,a condensing inorganic alkali, a compound of the generalformula:

NH--RNHX O i l v p whereinR represents a member .of the group-consistingof phenyl and substitutedphenyl radicals bound to the two N'H- groups ofthe formula in ortho positions, X represents'a member of the groupconsisting of phenyl and substituted phenyl radicals, Y represents asulfonic, acid group and Z represents a member of the group consistingof hydrogenand bromine.

6. The process whichcomprises stirring for 48 hours at room?temperature: a mixture of dilute 0M caustic sodamsolutionwith a solutionof the com pound of the formula:

7. The process which comprises feebly boiling for about 3 hours. amixtureof caustic soda solution with a solution of the compoundof theformula:

EGGERT. '1;-

HOaS NH.OO.CH;

NH 25 p SOaH

